4.8 Article

Lamellar-Twisting-Induced Circular Dichroism of Chromophore Moieties in Banded Spherulites with Evolution of Homochirality**

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 53, Issue 17, Pages 4450-4455

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201310078

Keywords

chirality; chromophores; crystal growth; helical structures; polymers

Funding

  1. National Science Council of the Republic of China, Taiwan [NSC 102-2633-M-007-002]

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Banded spherulites are formed by crystallization of a chiral polymer that is end-capped with chromophore. Induced circular dichroism (ICD) of the chromophore can be found in the crystallized chiral polymers, giving exclusive optical response of the ICD. The ICD signals are presumed to be driven by the lamellar twisting in the crystalline spherulites, and the exclusive optical activity is attributed to the chirality transfer from molecular level to macroscopic level. To verify the suggested mechanism, the sense of the lamellar twisting in the crystalline spherulite is determined using PLM for the comparison with the ICD signals of the chromophore in the electron circular dichroism spectrum. The conformational chirality of the chiral polymer is determined by the vibrational circular dichroism spectrum. On the basis of the chiroptical results, evolution of homochirality from helical polymer chains (conformational chirality) to lamellar twisting in the banded spherulite (hierachical chirality) is suggested.

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